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The photophysical properties of the free neutral radical galvinoxyl were studied by a combination of femtosecond time-resolved spectroscopy and quantum chemical calculations. The electronic absorption spectrum is dominated by an intense band at 430 nm that is ascribed to the D(9,10)← D(0) transitions. Upon photoexcitation at 400 nm, the population of the D(9,10) states decays within less than 200 fs to the electronic ground state. This ultrafast internal conversion does not involve intramolecular modes with large amplitude motion as the measured dynamics does not show any significant dependence on the environment, but is most probably facilitated by a high density of electronic states of different character. Depending on the solvent, a weak transient band due to the galvinoxylate anion is also observed. This closed-shell species, which is fluorescent although its deactivation is also dominated by non-radiative decay, is generated upon biphotonic ionization of the solvent and electron capture. The ultrashort excited-state lifetime of the galvinoxyl radical precludes photoinduced disproportionation previously claimed to be at the origin of the formation of both anion and cation., (This journal is © the Owner Societies 2012)